CN104132989A - Organic field-effect tube gas sensor based on mixed insulating layer and preparation method thereof - Google Patents
Organic field-effect tube gas sensor based on mixed insulating layer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic field-effect tube gas sensor based on a mixed insulating layer; the organic field-effect tube gas sensor comprises a substrate, a gate electrode, a the mixed insulating layer, an organic semiconductor layer, a source electrode and a drain electrode, the gate electrode is arranged on the substrate, the mixed insulating layer and the organic semiconductor layer are arranged on the gate electrode, the source electrode and the drain electrode are respectively arranged on the organic semiconductor layer; and the mixed insulating layer comprises zinc oxide nanoparticles and a polymer insulating material. A simple method of proportional mixing of a zinc oxide nanoparticle dispersion liquid and a polymer insulating material solution is used for preparation of the mixed insulating layer, when an organic field-effect tube with the mixed insulating layer is placed in a target gas environment, the gas reacts with the organic semiconductor layer, and the gas may penetrate into the surface of the organic semiconductor layer to effect with the zinc oxide nanoparticles to impact in the transmission and threshold voltage of current carriers in a conductive channel of the organic field-effect tube to change the organic field-effect tube performance so as to improve the gas response.
Description
Technical field
The invention belongs to sensor preparing technical field, particularly a kind of organic effect tubular construction gas sensor based on mix insulation layer and preparation method thereof.This gas sensor can be aided with suitable organic semiconductor layer by the interact variation of the organic field-effect tube device performance that cause of gas and mix insulation layer, can realize that multiple gases is highly sensitive, the detection of low cost and wide region.
Background technology
In the mankind's daily productive life, direct or indirect has discharged a lot of harmful gases in atmosphere, as ammonia, nitrogen dioxide, sulphuric dioxide, formaldehyde, sulfuretted hydrogen etc.These harmful gases are having a strong impact on the healthy of the mankind, high concentration go back entail dangers to life security.
In more than ten years in the past, researcher has been developed a large amount of gas sensors based on metal-oxide film, optical fiber and biomaterial.From principle of work, the gas sensor of main flow, mostly is resistance sensor in the market, by gas molecule, at film surface, is reacted and causes the variation of conductivity, passes through the variation of detection resistance value to realize the detection to gas concentration in macroscopic view.But not resistance-type is mainly by utilizing some physical influences and device property to realize the detection to gas, such as the change of electric capacity (C-V), characteristics such as the volt-ampere characteristic of schottky diode and Jin Shu – Yangization Wu – semiconductor field (MOSFET) threshold voltage variation.In based on transistorized sensor, gate voltage is because the impact of measured matter can produce slight variation, amplification due to transistor itself, will obtain and change obvious channel current, by detecting channel current, can realize the detection to test substance, compared to the resistance of more difficult monitoring, be easier to survey.
Along with the develop rapidly of organic electronics and in the application of sensor field, with organic field-effect tube (organic thin-film transistor, OTFT) chemical sensor forming for basis becomes a study hotspot of sensor field, is applied to the existing wide coverage of detection of inorganic and volatile organic compounds.Compare with traditional gas sensor, the advantage such as the gas sensor based on OTFT structure is highly sensitive except having, can use at normal temperatures, also there are several remarkable advantages:
1) utilizing transistor fundamental characteristics is the easy curent change detecting by the high resistance change transitions that is difficult to detect;
2) can regulate by the grid operating voltage of suitable selector the sensitivity of sensor;
3) multiparameter model more has identification and the analysis that utilizes gas;
4), by regulating easily the electrical property of sensor to the chemical modification of organic molecule, improve sensitivity;
5) organism pliability is good, can be crooked, be easy to make various shapes;
6) be easy to integratedly, can prepare large area sensor array, be convenient to integrated, microminiaturized future development.
Summary of the invention
The object of the invention is to overcome the shortcoming of traditional gas sensor, provide a kind of preparation technology simple, low production cost, can be used for that gas detects and a kind of organic field-effect tube gas sensor based on mix insulation layer that can multiparameter response and preparation method thereof.
Technical scheme of the present invention is:
Organic field-effect tube gas sensor based on mix insulation layer, comprise substrate, gate electrode, mix insulation layer, organic semiconductor layer, source electrode and drain electrode, on described gate electrode setting and substrate, mix insulation layer and organic semiconductor layer are arranged on gate electrode, and source electrode and drain electrode are arranged at respectively on organic semiconductor layer; Described mix insulation layer is comprised of Zinc oxide nanoparticle and insulating material of polymer.
Zinc oxide nanoparticle is dispersed in insulating material of polymer, and described gas sensor detects gas with various high selectivity high-responsivity by selecting different organic semiconductor layers, insulating material of polymer and Zinc oxide nanoparticle combination to realize.
Described gas sensor at least can detect a kind of in nitrogen dioxide, ammonia, sulfuretted hydrogen, sulphuric dioxide, formaldehyde.
Further, in described mix insulation layer, Zinc oxide nanoparticle and insulating material of polymer weight ratio are 1:1 – 1:10.
Further, described mix insulation layer thickness is 500nm – 2000nm, and described Zinc oxide nanoparticle diameter is 5nm – 50nm.
Further, described insulating material of polymer is a kind of in polystyrene, poly-а-methyl styrene, polymethylmethacrylate, polycarbonate, dimethyl silicone polymer, polyvinyl alcohol (PVA), polyvinylpyrrolidone or pla-pcl and the multipolymer between them.
Further, organic semiconductor layer is aphthacene, pentacene, 6, a kind of in the silica-based acetylene pentacene of 13 – bis-or three isopropyl ester, CuPc, Phthalocyanine Zinc, Cobalt Phthalocyanine, rubrene, six thiophene, polythiophene or fullerene, described organic semiconductor layer thickness is 2～100nm.
Further, gate electrode, source electrode and drain electrode are made by gold, silver, copper and alloy material thereof, and the thickness of source electrode and drain electrode is 10～100nm.
Further, described substrate is made by silicon chip, glass, thin polymer film or metal forming.
The preparation method of the organic field-effect tube gas sensor based on mix insulation layer, it comprises the following steps
1. first substrate is cleaned thoroughly, dry after cleaning;
2. at substrate surface, prepare gate electrode;
3. on described gate electrode, prepare mix insulation layer and insulation course is processed;
4. on described mix insulation layer, prepare organic semiconductor layer;
5. on described organic semiconductor layer, prepare source electrode and drain electrode.
Further, step 3. in, mix insulation layer is prepared by spin coating, roller coat, a kind of method of dripping in film, impression, printing or spraying.
Do further, step 2. 5. in, gate electrode, source electrode, drain electrode are prepared by a kind of method in chemical vapor deposition, serigraphy, printing or the spin coating strengthening by vacuum thermal evaporation, magnetron sputtering, plasma, described step 4. in, prepared by a kind of method that described organic semiconductor layer is the chemical vapor deposition that strengthens by plasma, thermal oxide, spin coating, vacuum evaporation, roller coat, drip in film, impression, printing or spraying.
Compared with prior art, the invention has the advantages that:
One, by Zinc oxide nanoparticle being introduced to insulation course/organic semiconductor bed interface, utilize zinc paste polar surface, change the polarity at insulation course/organic semiconductor interface, thereby improve the adsorptive power to gas molecule, reach the object of regulation and control interfacial dielectric layer to gas sensitization characteristic, realize the lifting of organic field-effect tube gas sensor detection performance;
Two, the relative and gas sensor of tradition based on zinc paste, the present invention can at room temperature work, and without heating source, has reduced device cost and energy resource consumption;
Three, mix insulation layer is formed by directly mixing by Zinc oxide nanoparticle dispersion liquid and polymer insulation layer solution, in preparation process, only polymer insulation layer material need be changed into mix insulation layer material, without other additional processes, technique is simple, easy to implement, and material compatibility is high;
Four, Zinc oxide nanoparticle is dispersed in polymer insulation layer, and the function film thickness of device remains unchanged, and process matching is high;
Five, Zinc oxide nanoparticle and required insulating material of polymer wide material sources, all realized suitability for industrialized production, simply in conjunction with organic layer material, just can realize the multiple gases detection of high-responsivity; Simultaneous oxidation zinc has good bio-compatibility, adopts mix insulation layer can reduce the pollution to environment, and this advantage is particularly important for the sensor of a large amount of uses;
Six, by adjusting organic semiconductor layer thickness and kind, can realize the technical indicators such as high response speed, high selectivity, can freely allocate according to the actual requirements;
Seven, device each several part all can adopt solwution method low temperature preparation, and to substrate without specific (special) requirements, reduced production cost, large-scale industrialized production preferably.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention;
Fig. 2 is the response curves of two kinds of different components of the present invention under different ammonia atmosphere, and device A is Zinc oxide nanoparticle/polymethylmethacrylate mix insulation layer, and device B is polymethylmethacrylate insulation course;
In figure: 1-substrate, 2-gate electrode, 3-Zinc oxide nanoparticle, 4-insulating material of polymer, 5-mix insulation layer, 6-organic semiconductor layer, 7-source electrode, 8-drain electrode.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
With reference to Fig. 1, a kind of organic field-effect tube gas sensor based on mix insulation layer of the present invention, comprise substrate 1, gate electrode 2, the mix insulation layer 5 being formed by Zinc oxide nanoparticle 3 and insulating material of polymer 4, on described gate electrode setting and substrate, mix insulation layer is connected with organic semiconductor layer, mix insulation layer and organic semiconductor layer are arranged on gate electrode, and source electrode and drain electrode are arranged on organic semiconductor layer respectively.Under the effect of Zinc oxide nanoparticle, improve to the full extent gas responsiveness.
Below specific embodiments of the invention:
Embodiment 1:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polymethylmethacrylate and Zinc oxide nanoparticle, and thickness is 1000nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 10wt%; polymethyl methacrylate solution mass ratio is 10wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and polymethyl methacrylate solution is 1:1.Organic semiconducting materials is pentacene, and thickness is 2nm, and source electrode 5 and drain electrode 6 are Au, and thickness is 10nm, and this structure can realize the effective detection to ammonia.
Preparation method is as follows:
1. the glass substrate 1 of the good gate electrode ITO of sputter is cleaned thoroughly, after cleaning, with drying nitrogen, dry up;
2. adopt spin-coating method on ITO, to prepare mix insulation layer 5;
3. adopt vacuum vapour deposition to prepare pentacene organic semiconductor layer 6;
4. adopt vacuum vapour deposition to prepare source electrode 7 and drain electrode 8.
Embodiment 2:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polymethylmethacrylate and Zinc oxide nanoparticle, and thickness is 500nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 0.5wt%; polymethyl methacrylate solution mass ratio is 5wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and polymethyl methacrylate solution is 1:1.Organic semiconducting materials is pentacene, and thickness is 2nm, and source electrode 5 and drain electrode 6 are Ag, and thickness is 100nm, and this structure can realize the effective detection to ammonia.
Preparation method is as embodiment 1.
Embodiment 3:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polymethylmethacrylate and Zinc oxide nanoparticle, and thickness is 2000nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 10wt%; polymethyl methacrylate solution mass ratio is 5wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and polymethyl methacrylate solution is 1:1.Organic semiconducting materials is pentacene, and thickness is 100nm, and source electrode 5 and drain electrode 6 are Cu, and thickness is 100nm, and this structure can realize the effective detection to ammonia.
Preparation method is as embodiment 1.
Embodiment 4:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polymethylmethacrylate and Zinc oxide nanoparticle, and thickness is 500nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 0.5wt%; polymethyl methacrylate solution mass ratio is 5wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and polymethyl methacrylate solution is 1:1.Organic semiconducting materials is pentacene, and thickness is 2nm, and source electrode 5 and drain electrode 6 are Ag, and thickness is 100nm, and this structure can realize the effective detection to ammonia.
Preparation method is as embodiment 1.
Embodiment 5:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polymethylmethacrylate and Zinc oxide nanoparticle, and thickness is 500nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 0.5wt%; polymethyl methacrylate solution mass ratio is 5wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and polymethyl methacrylate solution is 1:1.Organic semiconducting materials is CuPc, and thickness is 2nm, and source electrode 5 and drain electrode 6 are Au, and thickness is 100nm, and this structure can realize the effective detection to nitrogen dioxide gas.
Preparation method is as embodiment 1.
Embodiment 6:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polymethylmethacrylate and Zinc oxide nanoparticle, and thickness is 500nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 0.5wt%; polymethyl methacrylate solution mass ratio is 5wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and polymethyl methacrylate solution is 1:1.Organic semiconducting materials is six thiophene, and thickness is 2nm, and source electrode 5 and drain electrode 6 are Au, and thickness is 100nm, and this structure can realize effective detection of PARA FORMALDEHYDE PRILLS(91,95) gas.
Preparation method is as embodiment 1.
Embodiment 7:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polymethylmethacrylate and Zinc oxide nanoparticle, and thickness is 500nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 0.5wt%; polymethyl methacrylate solution mass ratio is 5wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and polymethyl methacrylate solution is 1:1.Organic semiconducting materials is six thiophene, and thickness is 2nm, and source electrode 5 and drain electrode 6 are Cu, and thickness is 100nm, and this structure can realize the effective detection to sulfur dioxide gas.
Preparation method is as embodiment 1.
Embodiment 8:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polymethylmethacrylate and Zinc oxide nanoparticle, and thickness is 500nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 10wt%; polymethyl methacrylate solution mass ratio is 10wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and polymethyl methacrylate solution is 1:1.Organic semiconducting materials is CuPc, and thickness is 100nm, and source electrode 5 and drain electrode 6 are Au, and thickness is 100nm, and this structure can realize the effective detection to nitrogen dioxide gas.
Preparation method is as embodiment 1.
Embodiment 9:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polyvinyl alcohol (PVA) and Zinc oxide nanoparticle, and thickness is 500nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 10wt%; poly-vinyl alcohol solution mass ratio is 10wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and poly-vinyl alcohol solution is 1:1.Organic semiconducting materials is the silica-based acetylene pentacene of 6,13 – bis-or three isopropyl ester, and thickness is 100nm, and source electrode 5 and drain electrode 6 are Au, and thickness is 100nm, and this structure can realize the effective detection to hydrogen sulfide gas.
Preparation method is as follows:
1. the glass substrate 1 of the good gate electrode ITO of sputter is cleaned thoroughly, after cleaning, with drying nitrogen, dry up;
2. adopt spin-coating method on ITO, to prepare mix insulation layer 5;
3. adopt spraying process to prepare the silica-based acetylene pentacene of 6,13 – bis-or three isopropyl ester organic semiconductor layer 6;
4. adopt vacuum vapour deposition to prepare source electrode 7 and drain electrode 8.
Embodiment 10:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polyvinyl alcohol (PVA) and Zinc oxide nanoparticle, and thickness is 2000nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 10wt%; poly-vinyl alcohol solution mass ratio is 10wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and poly-vinyl alcohol solution is 1:1.Organic semiconducting materials is the silica-based acetylene pentacene of 6,13 – bis-or three isopropyl ester, and thickness is 100nm, and source electrode 5 and drain electrode 6 are Au, and thickness is 100nm, and this structure can realize the effective detection to hydrogen sulfide gas.
Preparation method is with embodiment 7.
Embodiment 11:
Be illustrated in figure 1 bottom gate apical grafting touch structure; the material of each layer and thickness are: substrate 1 is glass; gate electrode 2 is ITO; thickness is 120nm; mix insulation layer 5 is for to be mixed by polyvinyl alcohol (PVA) and Zinc oxide nanoparticle, and thickness is 500nm, wherein Zinc oxide nanoparticle dispersion liquid mass ratio 10wt%; poly-vinyl alcohol solution mass ratio is 10wt%, and the blending ratio of Zinc oxide nanoparticle dispersion liquid and poly-vinyl alcohol solution is 1:1.Organic semiconducting materials is the silica-based acetylene pentacene of 6,13 – bis-or three isopropyl ester, and thickness is 100nm, and source electrode 5 and drain electrode 6 are Au, and thickness is 100nm, and this structure can realize the effective detection to hydrogen sulfide gas.
Preparation method is as follows:
1. the glass substrate 1 of the good gate electrode ITO of sputter is cleaned thoroughly, after cleaning, with drying nitrogen, dry up;
2. adopt spin-coating method on ITO, to prepare mix insulation layer 5;
3. adopt spin-coating method to prepare the silica-based acetylene pentacene of 6,13 – bis-or three isopropyl ester organic semiconductor layer 6;
4. adopt vacuum vapour deposition to prepare source electrode 7 and drain electrode 8.
The embodiment of the present invention is better embodiment, but its concrete enforcement is not limited to this, and those of ordinary skill in the art is very easily according to above-described embodiment; understand spirit of the present invention; and make different amplifications and variation, and only otherwise depart from the present invention, within all belonging to protection scope of the present invention.
Claims (10)
1. the organic field-effect tube gas sensor based on mix insulation layer, it is characterized in that, comprise substrate, gate electrode, mix insulation layer, organic semiconductor layer, source electrode and drain electrode, on described gate electrode setting and substrate, mix insulation layer and organic semiconductor layer are arranged on gate electrode, and source electrode and drain electrode are arranged at respectively on organic semiconductor layer; Described mix insulation layer is comprised of Zinc oxide nanoparticle and insulating material of polymer.
2. the organic field-effect tube gas sensor based on mix insulation layer according to claim 1, is characterized in that, in described mix insulation layer, Zinc oxide nanoparticle and insulating material of polymer weight ratio are 1:1 – 1:10.
3. the organic field-effect tube gas sensor based on mix insulation layer according to claim 1, is characterized in that, described mix insulation layer thickness is 500nm – 2000nm, and described Zinc oxide nanoparticle diameter is 5nm – 50nm.
4. the organic field-effect tube gas sensor based on mix insulation layer according to claim 1, it is characterized in that, described insulating material of polymer is a kind of in polystyrene, poly-а-methyl styrene, polymethylmethacrylate, polycarbonate, dimethyl silicone polymer, polyvinyl alcohol (PVA), polyvinylpyrrolidone or pla-pcl and the multipolymer between them.
5. the organic field-effect tube gas sensor based on mix insulation layer according to claim 1, it is characterized in that, organic semiconductor layer is aphthacene, pentacene, 6, a kind of in the silica-based acetylene pentacene of 13 – bis-or three isopropyl ester, CuPc, Phthalocyanine Zinc, Cobalt Phthalocyanine, rubrene, six thiophene, polythiophene or fullerene, described organic semiconductor layer thickness is 2～100nm.
6. the organic field-effect tube gas sensor based on mix insulation layer according to claim 1, it is characterized in that, gate electrode, source electrode and drain electrode a kind of the making in gold, silver or copper and alloy material thereof, the thickness of source electrode and drain electrode is 10～100nm.
7. the organic field-effect tube gas sensor based on mix insulation layer according to claim 1, is characterized in that, described substrate is made by silicon chip, glass, thin polymer film or metal forming.
8. according to the preparation method of the organic field-effect tube gas sensor based on mix insulation layer described in claim 1-7 any one, it is characterized in that, comprise the following steps:
1. first substrate is cleaned thoroughly, dry after cleaning;
2. at substrate surface, prepare gate electrode;
3. on described gate electrode, prepare mix insulation layer and insulation course is processed;
4. on described mix insulation layer, prepare organic semiconductor layer;
5. on described organic semiconductor layer, prepare source electrode and drain electrode.
9. the preparation method of the organic field-effect tube gas sensor based on mix insulation layer according to claim 7, is characterized in that, step 3. in, mix insulation layer is prepared by spin coating, roller coat, a kind of method of dripping in film, impression, printing or spraying.
10. the preparation method of the organic field-effect tube gas sensor based on mix insulation layer according to claim 7, it is characterized in that, step 2. 5. in, gate electrode, source electrode, drain electrode are prepared by a kind of method in chemical vapor deposition, serigraphy, printing or the spin coating strengthening by vacuum thermal evaporation, magnetron sputtering, plasma, step 4. in, prepared by a kind of method that described organic semiconductor layer is the chemical vapor deposition that strengthens by plasma, thermal oxide, spin coating, vacuum evaporation, roller coat, drip in film, impression, printing or spraying.
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| CN105334257A (en) * | 2015-11-25 | 2016-02-17 | 电子科技大学 | OFET (Organic Field Effect Transistor) ammonia gas sensor containing functional insulation layer |
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